Heteropoly salts or acid salts deposited in the interior of porous supports

ABSTRACT

The present invention relates to a catalyst composition, its methods of preparation and its use in aromatic alkylation processes. The composition comprises a heteropoly compound selected from the group consisting of heteropoly salts and heteropolyacid salts deposited in the interior of a porous support selected from the group consisting of silica, titania, and zirconia, wherein said salt of said heteropoly salt and said heteropolyacid salt is selected from the group consisting of ammonium, cesium, potassium, and rubidium salts and mixtures thereof, and wherein said heteropoly salt and said heteropolyacid salt are formed with a heteropolyacid selected from the group consisting of 12-tungstophosphoric, 12-tungstosilicic, 12-molybdophosphoric, and 12-molybdosilicic acid.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of U.S. Ser. No. 156,178, filed Nov. 19,1993, now abandoned.

FIELD OF THE INVENTION

Various catalysts have been used to alkylate phenols with olefins.Traditionally, such alkylation reactions were carried out at atmosphericpressure with the reactants and catalyst in the liquid phase, referredto as "homogeneous catalysis", utilizing catalysts such as sulfuricacid, boron trifluoride, and aluminum chloride. Alkylation of phenolswith olefins of up to 500,000 number average molecular weight have beendisclosed, such as in U.S. Pat. No. 4,735,582, and EP Publication440,507 A2. The drawback of homogeneous catalysis, of course, is thedifficulty and expense in removing the catalyst from the liquid product.In addition, the toxic and corrosive nature of the strong acid catalystsmentioned above presents environmental and operational problems.

12-tungstophosphoric acid (H₃ PW₁₂ O₄₀ ; HPW) has been shown to be aneffective catalyst in aromatic alkylations, capable for example ofalkylating phenol with olefinic polymers to produce important alkylphenol intermediates. HPW is very soluble in water (approximately 2 gmHPW/gm H₂ O at room temperature) and in other polar solvents. Evensupported HPW will solubilize. Although phenol is substantially lesspolar than water, it will solubilize some HPW (12-tungstophosphoricacid) at temperatures (130-170° C.) used to alkylate phenol and olefins.This limits the utility of the acid because it is consumed in a shorttime and contaminates the product. HPW has an approximate solubility of0.3-1.0% in phenol at 170° C. The cesium and ammonium salts or acidsalts of HPW are negligibly soluble in water at room temperature andphenol at reaction temperatures. However, these salts, when prepared bytechniques known in the prior art, form submicron (100 Å)water-insoluble particles which produce large pressure drops when usedin fixed bed applications. Furthermore by virtue of their insolubility,they cannot be deposited in the interior of porous supports by simplydissolving them in solution and impregnating; the classical prior arttechnique. It is readily apparent to those skilled in the art that, ifthe insoluble precipitates are produced outside of the support particle,they will form only a coating of the salt on the outer surface ofsupport particles, especially large extrudates since the particle sizeof the precipitate particle exceeds that of the pore diameter of thesupport material. The technique suffers from problems associated withattrition and adherence of the outer coating. What is needed in the artis a way of supporting the heteropoly salts or acid-salts deposited inthe interior of porous large particle carriers.

SUMMARY OF THE INVENTION

The present invention relates to a catalyst composition, its methods ofpreparation and its use in aromatic alkylation processes. The presentinvention relates to a novel catalyst composition comprising aheteropoly compound selected from the group consisting of heteropolysalts and heteropolyacid salts deposited in the interior of a poroussupport selected from the group consisting of silica, titania, andzirconia, wherein said salt of said heteropoly salt and saidheteropolyacid salt is selected from the group consisting of ammonium,cesium, potassium, and rubidium salts and mixtures thereof, and whereinsaid heteropoly salt and said heteropolyacid salt are formed with aheteropolyacid selected from the group consisting of12-tungstophosphoric, 12-tungstosilicic, 12-molybdophosphoric, and12-molybdosilicic acid.

The invention is further directed to the method of preparing catalystcompositions comprising the steps of:

(a) impregnating a soluble precursor into a support selected from thegroup consisting of silica, titania, and zirconia, wherein said solubleprecursor is selected from the group consisting of a heteropolyacid, the100-250° C. hydrothermal reaction product of ammonium metatungstate withammonium phosphate dibasic, the 150° C. hydrothermal reaction product ofammonium molybdate with ammonium phosphate dibasic, a solution of amixture of urea and a heteropolyacid, a water soluble cesium salt, awater soluble Rb salt, and a water soluble K salt, wherein saidheteropolyacids are selected from the group consisting of12-tungstophosphoric acid, 12-tungstosilicic acid, 12-molybdophosphoricacid and 12-molybdosilicic acid;

(b) drying said silica support having said soluble precursor impregnatedtherein at about 90 to about 130° C.;

(c) thermally treating said dried support at about 200 to about 350° C.wherein when said soluble precursor is a heteropolyacid, a source ofammonia gas is passed over the dried support at a temperature of about100-150° C. followed by thermal treatment;

(d) impregnating said thermally treated support with a heteropolyacidwhen said soluble precursor selected from the group consisting of awater soluble cesium, rubidium and potassium salt followed by drying atabout 90 to about 150° C. and calcination at about 200 to about 350° C.and wherein said heteropolyacid is selected from the group ofheteropolyacids of step (a) resulting in the deposition of the salt oracid-salt in the interior of the porous support.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the x-ray diffraction spectra of bulk and silica supportedammonium salts of 12-tungstophosphoric acid. The x axis is two theta(degrees) and the y axis is relative intensity. Lines A, B, C, D, and Edepict bulk 12-tungstophosphoric acid, bulk (NH₄)_(3-x) H_(x) PW₁₂ O₄₀,24.3% (NH₄)_(3x) H_(x) PW₁₂ /SiO₂ prepared via a reaction of H₃ PW₁₂ O₄₀·6H₂ O and NH₃ gas, 24.3% (NH₄)_(3-x) H_(x) PW₁₂ /SiO₂ prepared via anautoclave preparation, and 40% (NH₄)_(3-x) H_(x) PW₁₂ /SiO₂ prepared viaimpregnation and calcination of an urea and 12-tungstophosphoric acidsolution, respectively, wherein x is equal to or less than 0.5. Thesilica in all of the preparations has a surface area of 270 m² /g.

FIG. 2 shows the x-ray diffraction spectra of bulk and silica supportedcesium acid salts of 12-tungstophosphoric acid. The x axis is two theta(degrees) and the y axis relative intensity. Lines A, B, and C depictbulk 12-tungstophosphoric acid, bulk Cs₂.5 H₀.5 PW₁₂ O₄₀ and 40% Cs₂.5H₀.5 PW₁₂ O₄₀ /SiO₂ prepared by sequential impregnation and in situreaction.

FIG. 3, views A, B, C, and D, shows that the cesium catalysts of theinstant invention form what is referred to in the art as an egg whitecatalyst. The pictures are of a cross-sectional view of a cesium acidsalt catalyst prepared in accordance with the instant invention.

DETAILED DESCRIPTION OF THE INVENTION

Heteropoly acids form by condensation of two or more oxyacids, e.g.,phosphoric or silicic acid with tungstic acid, and contain largepolyoxometallate anions with interstitial hydrated protons and variablelevels of water of hydration. The heteropoly acids are soluble in wateror polar oxygenated hydrocarbons, such as alcohols or ethers. Theparticular heteropoly acids of the present catalysts contain anionsadopting the well known Keggin structure and are represented byformulas: H₃ PW₁₂ O₄₀ ·6H₂ O (phosphotungstic acid also referred to as12-tungstophosphoric acid. H₄ SiW₁₂ O₄₀ ·6H₂ O (12-tungstosilicic acidor silicotungstic acid), H₃ PMo₁₂ O₄₀ ·6H₂ O (12-molybdophosphoricacid), and H₄ SiMo₁₂ O₄₀ ·6H₂ O (12-molybdosilicic acid). They containe.g., a central tetrahedral PO₄ or SiO₄ group connected to 12surrounding WO₆ octahedra and can be considered e.g., the condensationproduct of phosphoric acid with tungstic acid or phosphoric acid withsilicic acid, etc.

Although such water soluble heteropoly acids can be readily deposited onsupports by impregnation techniques, their Cs, NH₄, K and Rb saltcounterparts are water insoluble and current means for impregnating themonto supports or into the interior of the porous supports are unknown.The current invention describes a way of preparing support catalystwherein such insoluble salts or acid salts are deposited in the interiorof porous supports.

The instant invention encompasses both heteropoly salts andheteropolyacid salts. During the preparation of the catalysts, aheteropolyacid is employed and in situ formation of the salt or acidsalt occurs. In the instant invention at least 1.5 protons of the acidwill be exchanged and up to three protons may be exchanged with thedesignated cations for heteropoly acids containing 3 protons. If lessthan three protons are exchanged the acid salt will be formed, if all(3) of the protons are exchanged, the salt will be formed. For cesiumcatalysts, exchange of 2.5 protons is preferred. For heteropolyacidscontaining 4 protons, at least 2.5 protons of the acid will be exchangedand up to 4 protons may be exchanged. If all 4 are exchanged, the saltresults. If 2.5 to 3.9 protons are exchanged, the acid salt results.

The preferred support utilized in the present invention is a highsurface area porous silica support. Such supports are commerciallyavailable or may be prepared by well known techniques. Preferably thesupport will be thermally treated prior to use. For example, the silicamay be calcined at about 500° C. The silica support utilized will be onepreferably useable for fixed-bed reactions. Therefore, it is preferablethat the silica be present in the form of extrudates although otherforms are possible. Additionally the instant catalysts can be used influidized bed systems. Hence, the particle size of the support can rangefrom 0.1 mm powder to 1/8"×1/2" extrudates and 1 to 3 mm diameterspheres. Other supports utilizable are supports that will allow theheteropoly salt or acid salt to retain its structure as microcrystallites within the pore structure of the porous support, e.g., ZrO₂and TiO₂.

The salts of the invention have the general formula H_(3-x) M_(x) PQ₁₂O₄₀ where x=3, M=K, Cs, Rb and H_(4-x) M_(x) SiQ₁₂ O₄₀ where x=4, M=Cs,K, Rb, NH₄. Q=tungsten or molybdenum in each of the above formulas. Theacid salts have the same general formulas except that x=1.5 to 2.9inclusive and 2.5 to 3.9 inclusive, respectively.

As used in the instant invention, the heteropoly acids are converted totheir corresponding salts or acid salts. Suitable salts include thesalts of ammonium, cesium, potassium, rubidium and mixtures thereof withammonium and cesium being preferred. The salt cations substitute forfrom 1.5 to 2.9 of the protons of the heteropoly acid in a heteropolyacid containing three hydrogens. For example:

    H.sub.3 PW.sub.12 O.sub.40 ·6H.sub.2 O=(H.sub.5 O.sub.2).sup.+.sub.3PW12 O.sub.40

can be exchanged with ammonium to the salt

    (NH.sub.4).sub.3 PW.sub.12 O.sub.40

or acid salt. Representative of two acid salts are

    (NH.sub.4).sub.2.5 H.sub.0.5 PW.sub.12 O.sub.40 or (NH.sub.4).sub.2 HPW.sub.12 O.sub.40

The amount of heteropoly acid salt or heteropolysalt incorporated ontothe silica support will range from 2 to 60 wt %, preferably 10 to 40 wt%.

The catalysts of the present invention are prepared by impregnating awater soluble precursor into the interior of a porous support such asporous silica and then converting the precursor in situ into the desiredheteropoly acid salt or heteropoly salt. The soluble precursors includea heteropolyacid, a mixture of urea and a heteropolyacid, a watersoluble cesium, rubidium or potassium salt, and the 100 to 250° C.hydrothermal reaction product of ammonium metatungstate or ammoniummolybdate with ammonium phosphate dibasic. The impregnated supports arethen dried at 90 to about 130 followed by calcination at about 200 toabout 350° C. When the soluble precursor is a heteropolyacid, theimpregnated support is contacted with ammonia during the drying step. Inthe case of a soluble cesium, rubidium or potassium salt as the solubleprecursor, following drying and calcination the impregnated support isreimpregnated with a heteropolyacid and the drying and calcination stepsare repeated. Thus, the desired heteropoly salt or heteropolyacid saltis formed in situ in the interior of the porous support.

In the case of cesium containing catalysts, the cesium acid salt ispresent in a zone remote from both the center and the external surfaceof the support, which can be described as a catalytically active ring ofabout 10 to about 20 microns thick present within the interior of thesupport. Such a catalyst is referred to in the art as an egg whitecatalyst (see "Theory of Preparation of Supported Catalysts," Neimark,et al., Ind. Eng. Chem. Prod. Res. Dev. 1981, 20, 439-450). Refer toFIG. 3.

Specifically, incorporation of the ammonium heteropoly acid salt onto asilica support can be achieved in the following ways. The desiredheteropoly acid may first be incorporated onto the silica support bywell known techniques. The supported heteropoly acid is then treatedwith a gaseous mixture of ammonium in nitrogen for a time and at a spacevelocity sufficient to titrate substantially all of the protons of theheteropoly acid with NH₃. For example a 5% NH₃ /N₂ gaseous mixturetreatment at 150° C. can be used. Such treatment criteria are readilydeterminable.

Secondly, it has been found that a soluble precursor can be formed byhydrothermally reacting ammonium metatungstate and ammonium phosphatedibasic in a 12W/1P (12 tungsten/1 phosphorus) molar ratio. Thematerials are dissolved in water and heated in an autoclave to 150° C.overnight followed by impregnation onto silica. Subsequent drying andcalcination then form the heteropolysalt desired.

Alternatively, urea may be added to HPW (12-tungstophosphoric acid) in amole ratio of urea to HPW of 0.5 to 2/1 and impregnated onto silica,followed by calcination at 400° C.

Cesium catalysts may be prepared via sequential impregnation techniquesand in situ reaction. Such techniques involve first reacting solublecesium salt onto, e.g., a silica support, drying and calcining, followedby impregnation with the soluble heteropoly acid, drying and calcining.Such materials appear to be the result of an in situ reaction betweenthe cesium salt and the acid on the support. Suitable cesium salts areany water soluble cesium salts such as cesium carbonate and cesiumnitrate. Drying is conducted between about 90 and 150° C. and calciningbetween about 200 and 350° C.

The invention is further directed to the use of the instant catalysts inan aromatic alkylation process. The aromatic starting material foraromatic alkylation can be benzene, phenol, toluene or a combination ofthe three. Olefinic starting materials include olefins of C₂ up to andincluding olefins having a molecular weight of 5000. For example, on thevery low end, olefins such as ethylene or propylene would be suitable,polymeric olefins could be used as well. Generally, the heteropolycatalyst will be charged to provide at least about 0.001, preferablyfrom 0.1 to 0.9, more preferably from 0.05 to 0.4, moles of catalyst permole of polymer alkylating agent charged to the alkylation reactionzone. Use of greater than 1 mole of the inorganic catalyst per mole ofpolymer alkylating agent is not generally required.

The temperature for alkylation can also vary widely, and will typicallyrange from 20 to 250° C., preferably from 30 to 200° C., more preferablyfrom 100 to 180° C.

For phenol alkylation with a polymeric olefin, the reaction temperaturewill also affect the ratio of para-substituted to ortho-substitutedreaction product. Reaction temperatures about 130° C. will favor nearlyequal amounts (i.e., racemic) of ortho- and para-substituted alkylatedaromatic, anywhere from about 40 to 60% by weight of one to 60 to 40% byweight of the other. Very little disubstituted alkylated aromatic hasbeen found at any of the temperatures tested. Reaction temperaturesbelow 130° C. yield increasing proportions of para-substituted product.The actual temperature at which the transition occurs depends upon themolecular weight of the alkylating agent.

For industrial purposes a preferred temperature range is from about 150°C. to about 250° C. At these temperatures, the polymer alkylating agentis an easy to handle liquid, the reaction occurs rapidly, and theproduct mixture is approximately racemic.

The alkylation reaction time can vary and will generally be from 0.5 to5 hours, although longer or shorter times can also be employed. Thealkylation process can be practiced in a batchwise, continuous orsemicontinuous manner.

The reaction may be carried out with or without a solvent. The solventsmay be polar or non-polar with the proviso that they are not to beprotic. Non-polar solvents are preferred since solvents of high enoughpolarity, even if non-protic, may cause partial or complete dissolutionof the catalyst. Hence, preferred solvents include the aliphatichydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons,etc.

Preferred solvents are those sufficiently less volatile than water,under the reaction conditions utilized, so as to allow water to bedriven out of the reaction mixture with minimal loss of solvent. Suchsolvents include the hydroxyaromatic reactants themselves as well as thedichlorobenzenes (ortho, meta, and para), heptane, decane, and the like.

For mass production it is preferred that a continuous process beutilized. This involves continuously introducing reactants and solventsinto a reaction zone and continuously drawing off the products of thereaction. Hence, it is advantageous to use extrudates as is possiblewith the present invention. Although the unsupported NH₄ and Cs acidsalts are known in the art to work as catalysts, they could not beprepared as extrudates as the present acid salts and salts deposited inthe interior of porous support extrudates can.

Means for either retaining the catalyst in the reaction zone arepreferred, otherwise means for separating the catalyst from the producteffluent and recycling it back to the reaction zone are required.

EXAMPLES Example 1.

8.1% (NH₄)_(3-x) H_(x) PW₁₂ O₄ /SiO₂ powder (Davison 62), wherein x isequal to or less than 0.5.

Catalyst Preparation: autoclave preparation of supported ammonium salt:45.6 grams of ammonium metatungstate (92.2% WO₃) was dissolved alongwith 2.0 grams of ammonium phosphate dibasic in 120 cc of water. Thesolution was placed in a 300 cc autoclave, stirred, and the temperaturewas raised to 150° C. over a period of 5 hours and held at thistemperature for 2.5 hours. After the autoclave was cooled, a clearsolution weighing 160 gm was removed. 12.8 grams of this solution wastaken and water was added to give a total volume of 50 cc. This solutionwas impregnated to the point of incipient wetness onto a silica powder(Davison 62) precalcined at 600° C. overnight and possessing a surfacearea of 270 m² /g. The sample was then dried at 120° C. and calcined at300° C. for 3 hours. A second catalyst was prepared corresponding to24.3% (NH₄)_(3-x) H_(x) PW₁₂ O₄₀ /SiO₂ by impregnating 40 grams ofDavison 62 silica with 46.4 grams of the autoclave liquid to which wateris added to give a total volume of 50 cc. This catalyst was also driedat 120° C. overnight and calcined at 300° C. for three hours. FIG. 1shows the X-ray diffraction spectra of the 24.3% (NH₄)_(3-x) H_(x) PW₁₂O₄₀ /SiO₂ catalysts compared to the parent 12-tungstophosphoric acid andthe conventionally prepared bulk (NH₄)_(3-x) H_(x) PW₁₂ O₄₀ salt andshows that the impregnated autoclave reaction product produces asupported ammonium salt on drying and calcination.

Example 2

Silica supported cesium acid salt: 30% Cs₂.5 H₀.5 PW₁₂ O₄₀ /SiO₂ bysequential impregnation (Davison 62 silica powder).

Catalyst Preparation: 40 grams of a Davison 62 powder silica meshed to60/80 size and precalcined at 600° C. overnight was selected. 2.16 gramsof cesium carbonate was dissolved in 55 cc H₂ O and this solution wasimpregnated to the point of incipient wetness onto the silica powder.The sample was then dried at 120° C., and calcined at 300° C. for 3hours. A solution of 15.96 grams of H₃ PW₁₂ O₄₀ ·6H₂ O which wasprepared from a commercial supply (Allan Chemicals) by drying at 120° C.was then dissolved in 55 cc of H₂ O and impregnated by incipient wetnessonto Cs-impregnated silica, dried overnight at 120° C. and calcined at300° C. for three hours. To check that all the 12-tungstophosphoric acidreacted to form the insoluble Cs-acid salt, the product was immersed ina sufficient quantity of water to completely cover it, stirred forseveral minutes and filtered. The filtrate was retained, and dried, butno solid crystallized from the solution, indicating that no soluble acidwas still present on the silica. A similar sample of 40% loading wasprepared analogously. Also, bulk (unsupported) Cs₂.5 H₀.5 PW₁₂ O₄₀ wasprepared as described in the prior art by adding a cesium carbonatesolution to a solution of the 12-tungstophosphoric acid and forming afine water-insoluble precipitate. FIG. 2 shows the X-ray diffractionspectra of the conventional bulk Cs-acid salt and the 40% Cs-acid saltsupported on silica. From these spectra, it is clear that this techniqueproduces the cesium acid salt supported on the silica powder.

Example 3

40% Cs₂.5 H₀.5 PW₁₂ O₄₀ /SiO₂ by sequential impregnation (1/16" diametersilica extrudates 260 m² /g.

Catalyst Preparation: 40 grams of 1/16" silica extrudates measuringbetween 1/8 and 3/8" long were precalcined at 600° C. overnight. Thesilica had a surface area of 260 m² /g. 3.39 grams of cesium carbonatewas dissolved in 44 cc H₂ O and this solution was impregnated to thepoint of incipient wetness. The sample was then dried at 120° C., andcalcined at 300° C. for 3 hours. A solution of 24.9 grams of H₃ PW₁₂ O₄₀·6H₂ O, which was prepared from a commercial supply (Allan Chemicals) bydrying at 120° C. was then dissolved in 44 cc of H₂ O and impregnated byincipient wetness onto the Cs-impregnated extrudate, dried overnight at120° C. and calcined at 300° C. for three hours. The X-ray diffractionspectra of the ground extrudate looked similar to the one described inexample two for the powder silica catalyst confirming that the Cs-acidsalt was formed supported on the extrudate.

Back-scattered electron images (see FIG. 3) of extrudates that had beensnapped perpendicular to their longitudinal axis were collected andshowed that typically the Cs-acid salt was located in an internal ringin an eggwhite configuration with more than 50% of the acid salt beingpresent in the ring. The typical ring diameter was on the order of 10microns. Therefore it is seen that, the acid-salt had been successfullydeposited into the interior of the large silica particle.

Example 4

A series of strong acid catalysts were compared with the cesium acidsalt of 12-tungstophosphoric acid for the alkylation of mesitylene withcyclohexene. 0.5 gm of catalyst freshly calcined at the temperaturesindicated to remove adsorbed water were loaded with 150 cc oftrimethylbenzene into a 250 cc autoclave, pressurized to 15 psi N₂ andheated to 100° C. while stirring at 600 rpm. When the temperatureequilibrates at 100° C., the stirring is stopped, the autoclavedepressurized, and 8 cc of cyclohexene are injected by syringe into theautoclave. Mixing is resumed and the autoclave repressurized to 15 psi.Samples are periodically withdrawn at 1, 15, 30, 45, 60, 90, and 120minute intervals. The one minute sample is used to calculate feedcomposition. All samples are analyzed by gc. Table 1 shows theconversions measured after two hours of reaction.

                  TABLE 1    ______________________________________                                         %                                         cyclo-                                         hexene                    wt.        Calcination                                         Conver-                    catalyst   Temperature                                         sion    Catalyst        (grams)    (°C.)                                         (2 hr)    ______________________________________    amorphous SiO.sub.2 --Al.sub.2 O.sub.3                    0.5        500       0.8    (75 wt % SiO.sub.2 ;25% Al.sub.2 O.sub.3)    H-mordenite     0.5        450       1.2    bulk 12-tungstophosphoric acid                    0.5        120       1.1    H.sub.3 PW.sub.12 O.sub.40.6H.sub.2 O (HPW)    bulk ammonium acid-salt of 12-                    0.5        300       28    tungstophosphoric acid    (NH.sub.4).sub.3-x H.sub.x PW.sub.12 O.sub.40    ZrO.sub.2 /SO.sub.4                    0.5        575       1.2    24% HPW/SiO.sub.2                    2.06 equivalent                               300       98                    to (0.5 gm                    HPW)    Cs.sub.2.5 H.sub.5 PW.sub.12 O.sub.40 (bulk)                    0.5        300       90    ______________________________________

Tables 1 and 2 show that both the Cs-acid salt and 12-tungstophosphoricacid supported on silica were the most active catalysts for mesitylenealkylation. For alkylation reactions that contain a polar reactant suchas phenol, the Cs acid salt is the preferred catalyst because of itslower solubility.

Example 5

Four catalysts were compared for the alkylation of mesitylene withcyclohexene. All catalysts were calcined at 300° C. prior to use.Catalyst C and D are the subject of this invention and described inExample 3. The reaction was carried out as described in Example 4.

                  TABLE 2    ______________________________________                    Wt. Catalyst % Cyclohexene    Catalyst        (grams)      Conversion (2 Hr)    ______________________________________    A   24% HPW/SiO.sub.2                        2.06 (equivalent to                                     98                        0.5 gm HPW)    B   Cs.sub.2.5 H.sub..5 PW.sub.12 O.sub.40 (bulk)                        0.5          90    C   40% Cs.sub.2.5 H.sub..5 PW.sub.12 O.sub.40 /                        1.25 (equivalent to                                     91        SiO.sub.2 powder (270 m.sup.2 /g);                        0.5 gm        ≅0.1-0.2 mm particle size                        Cs.sub.2.5 H.sub..5 PW.sub.12 O.sub.40)    D   40% Cs.sub.2.5 H.sub..5 PW.sub.12 O.sub.40 /                        1.25 (equivalent to                                     38        SiO.sub.2 extrudates (12/16"                        0.5 gm        diameter; 280 m.sup.2 /g                        Cs.sub.2.5 H.sub..5 PW.sub.12 O.sub.40)    ______________________________________

Table 2 shows that the supported cesium acid salt made by the techniquedescribed herein is effective in mesitylene alkylation. The Cs-acid salton the silica powder has the same activity as the bulk Cs acid salt pergram of acid salt. The activity of the extrudate is slightly lower dueto diffusional restrictions of the reactants entering into the largeparticle extrudate.

Example 6

9 grams of the catalyst of Example 1 consisting of 24% (NH₄)_(3-x) H_(x)PW₁₂ O₄₀ /SiO₂ was mixed with 72 gm dichlorobenzene and 28 gm of phenol.The mixture was heated to 170° C. and held for 5 hours at which time theliquid was extracted and tested for tungsten content. 5.4 gm of acomparative sample of 12.2% HPW/SiO₂ was mixed with 14.2 gm phenol and39.2 gm of dichlorobenzene and heated under similar conditions andanalyzed. The results are shown below:

    ______________________________________    Catalyst       Solubility in phenol/DCB at 170° C.    ______________________________________    12% HPW/SiO.sub.2                   3100 ppm    24% (NH.sub.4).sub.3-x H.sub.x PW.sub.12 O.sub.40                    194 pm    ______________________________________

Consequently the supported ammonium phosphotungstate salt is appreciablyless soluble than the supported acid. Similar results are found with thesupported Cs-acid salt.

Example 7

Reaction test: 50 grams of an ethylene-butene copolymer containing about46.9% ethylene with a vinylidene double bond content of 47% and anaverage molecular weight of 3670 were mixed with 28 grams of phenol, 25grams of o-dichlorobenzene as solvent, and 25 grams of the 8 wt %(NH₄)_(3-x) H_(x) PW₁₂ O₄₀ /SiO₂ (Davison 62)-catalyst described above.The reactants and catalyst were charged into a four necked roundbottomed flask equipped with an air stirrer, thermometer, condenser andnitrogen blanket and the reaction was carried out at 175° C. for a totaltime of 6 hours. After two hours a sample was withdrawn, filtered andstripped and analyzed for 58.1% alkylated phenol and after six hours thesample showed 68.6% conversion to alkylated phenol.

Example 8

Same catalyst as Example 3.

17583-130: 40 grams of the polymer of Example 7 were charged into areaction flask and mixed with 23 grams of phenol and 50 grams of theExample 3 catalyst (freshly calcined at 300° C., 1 h)--no solvent wasadded. The reaction mixture was then heated to 175° C. for 6 hours undermixing. The samples analyzed for: 64.3% conversion to alkylate at 2hours and 71.8 at 6 hours.

Example 9

Reaction Test: 50 grams of an ethylene-butene copolymer containing about46.9% ethylene, 39% vinylidene double bonds and an average molecularweight of 3670 were mixed with 15 grams of phenol, 25 grams of n-decaneas solvent and 34 grams of the 30% Cs₂.5 H₀.5 PW₁₂ O₄₀ /SiO₂ catalyst ofExample 2. The reaction mixture was then heated to 150° C. whilestirring under a nitrogen blanket for a period of 6 hours. The two hoursample analyzed for 64.9% alkylated phenol and the six hours sampleshowed 75.8% conversion to the alkylate.

What is claimed is:
 1. A catalyst composition comprising a heteropolycompound selected from the group consisting of heteropoly salts andheteropolyacid salts deposited in the interior of a porous supportselected from the group consisting of silica, zirconia and titania,wherein said salt of said heteropoly salt and said heteropolyacid saltis selected from the group consisting of ammonium, cesium, potassium,and rubidium salts and mixtures thereof, and wherein said heteropolysalt and said heteropolyacid salt are formed with a heteropolyacidselected from the group consisting of 12-tungstophosphoric,12-tungstosilicic, 12-molybdophosphoric, and 12-molybdosilicic acid. 2.A catalyst composition according to claim 1 wherein said heteropolycompound is the ammonium salt or acid-salt of 12-tungstophosphoric acidand said support is silica.
 3. A catalyst composition according to claim1 wherein said heteropoly compound is the cesium acid salt of12-tungstophosphoric acid and said support is silica.
 4. A catalystcomposition according to claim 1 wherein said heteropoly compound ispresent in an amount of about 2 to about 60 wt %.
 5. The catalystcomposition of claim 1 wherein the support material has a size in therange from 0.1 mm powders to 1/8"×1/2" extrudates, and 1 to 3 mmdiameter spheres.
 6. The catalyst composition of claim 5 wherein thesupport is silica extrudate.
 7. The catalytic composition of claim 1wherein when the acid salt is cesium and the support is a porous silicaparticle the cesium acid salt is distributed in an egg whitedistribution in the interior of the particle.
 8. A method of preparing acatalyst composition comprising the steps of:(a) impregnating a solubleprecursor into a support selected from the group consisting of silica,titania, and zirconia, wherein said soluble precursor is selected fromthe group consisting of a heteropolyacid, the 100-250° C. hydrothermalreaction product of ammonium metatungstate with ammonium phosphatedibasic, the 150° C. hydrothermal reaction product of ammonium molybdatewith ammonium phosphate dibasic, a solution of a mixture of urea and aheteropolyacid, a water soluble cesium salt, a water soluble Rb salt,and a water soluble K salt, wherein said heteropolyacids are selectedfrom the group consisting of 12-tungstophosphoric acid,12-tungstosilicic acid, 12-molybdophosphoric acid and 12-molybdosilicicacid; (b) drying said silica support having said soluble precursorimpregnated therein at about 90 to about 130° C.; (c) thermally treatingsaid dried support at about 200 to about 350° C. wherein when saidsoluble precursor is a heteropolyacid, a source of ammonia gas is passedover the dried support at a temperature of about 100-150° C. followed bythermal treatment; (d) impregnating said thermally treated support witha heteropolyacid when said soluble precursor selected from the groupconsisting of a water soluble cesium, rubidium and potassium saltfollowed by drying at about 90 to about 150° C. and calcination at about200 to about 350° C. and wherein said heteropolyacid is selected fromthe group of heteropolyacids of step (a) thereby resulting in thedeposition of the heteropoly salt or heteropoly acid salt in theinterior of the porous support.
 9. An aromatic alkylation processcomprising contacting at aromatic alkylation conditions a catalystcomposition comprising a heteropoly compound selected from the groupconsisting of heteropoly salts and heteropolyacid salts deposited in theinterior of a porous support selected from the group consisting ofsilica, titania, and zirconia, wherein said salt of said heteropoly saltand said heteropolyacid salt is selected from the group consisting ofammonium, cesium, potassium, and rubidium salts and mixtures thereof,and wherein said heteropoly salt and said heteropolyacid salt are formedwith a heteropolyacid selected from the group consisting of12-tungstophosphoric, 12-tungstosilicic, 12-molybdophosphoric, and12-molybdosilicic acid with a feed comprising an aromatic compoundselected from the group consisting of benzene, toluene, and phenol withan olefin selected from the group consisting of C₂ to olefins having amolecular weight up to 5000 inclusive.
 10. A catalyst compositionaccording to claim 1 wherein said heteropoly salts and heteropoly acidsalts are deposited in the interior of said porous support in an eggwhite configuration.